CN116154273A - Binary co-doped sulfur silver germanium ore type solid electrolyte and preparation and application thereof - Google Patents

Binary co-doped sulfur silver germanium ore type solid electrolyte and preparation and application thereof Download PDF

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CN116154273A
CN116154273A CN202211543685.5A CN202211543685A CN116154273A CN 116154273 A CN116154273 A CN 116154273A CN 202211543685 A CN202211543685 A CN 202211543685A CN 116154273 A CN116154273 A CN 116154273A
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solid electrolyte
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lithium
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germanium ore
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段华南
李国耀
郑鸿鹏
吴绍平
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Shanghai Jiaotong University
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    • H—ELECTRICITY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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Abstract

The invention relates to a binary co-doped sulfur silver germanium ore type solid electrolyte and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly mixing lithium sulfide, phosphorus pentasulfide and lithium halide (LiX) and then grinding uniformly to obtain a solid electrolyte with a stoichiometric ratio of Li 6‑x PS 5‑x X 1+x Adding the mixed material with x being more than or equal to 0 and less than or equal to 1, and then adding the doping raw material and grinding uniformly to obtain mixed powder; then the mixed powder is sintered, kept warm and cooled to room temperature, and ground again to obtain the standard cubic phase binary co-doped sulfur silver germanium ore type solid electrolyte powder, wherein the binary co-doped two elements come from different compounds, respectively at P 5+ Cation M with position doped ion radius larger than that of phosphorus ion n+ In S 2‑ Site-doping anions Y z‑ . Compared with the prior art, the method for preparing the binary co-doped sulfur silver germanium ore type solid electrolyte can effectively enhance doping elements in the sintering processThe diffusion of impurities is avoided, and the sulfur silver germanium ore type solid electrolyte with high ionic conductivity, high air stability and high stability to metallic lithium is obtained.

Description

Binary co-doped sulfur silver germanium ore type solid electrolyte and preparation and application thereof
Technical Field
The invention belongs to the technical field of lithium battery electrolytes, and particularly relates to a binary co-doped sulfur silver germanium ore type solid electrolyte, and preparation and application thereof.
Background
Commercial lithium ion batteries have potential safety hazards due to the use of liquid electrolytes containing flammable organic solvents. Development of all-solid-state lithium batteries is one of the possible technical approaches to improve the safety of batteries. Among various solid electrolyte materials, sulfides are receiving extensive attention and research due to their ultra-high lithium ion conductivity and good processability. For example, a representative sulfide solid electrolyte such as 70Li 2 S-30P 2 S 5 、Li 10 GeP 2 S 12 、Li 9.54 Si 1.74 P 1.44 S1 1.7 Cl 0.3 And Li (lithium) 5.4 PS 4.4 Cl 1.6 The lithium ion conductivities of (sulfur silver germanium ore type) can reach 17, 25, 12 and 8.4mS cm respectively -1 Equivalent to a liquid electrolyte. The sulfur silver germanium ore-type sulfide does not generate serious interface reaction when being contacted with metallic lithium, does not use expensive raw materials, and can be processed into an ultrathin electrolyte membrane, so that the sulfide is considered to be one of solid electrolytes which are most promising to replace liquid electrolytes.
However, all-solid-state battery development based on sulfur silver germanium ore-type sulfides is still limited in the following two aspects. Firstly, sulfur silver germanium ore type sulfides have poor tolerance to water due to P in the crystal structure 5+ The high affinity to oxygen, the water in the air can easily attack and combine weaker P-S bond, poisonous hydrogen sulfide gas can be generated, and the electrochemical performance of the sulfur silver germanium ore type sulfide after the reaction with water is seriously reduced; in addition, theoretical and experimental results show that the electrochemical window of the sulfide silver germanium ore type sulfide is very narrow<2.2V), the interfacial instability will severely affect the capacity release and the service life of the all-solid-state battery when the positive and negative electrodes are matched. Therefore, on the premise of not sacrificing the conductivity of lithium ions, the method has important significance for improving the water stability of the sulfur silver germanium ore type sulfide and enhancing the compatibility of the sulfide with a metal lithium electrode.
Elemental doping or substitution is a viable and versatile method of designing sulfur silver germanium ore-type sulfides with uniform composition, structure, properties, and even versatility. Oxygen substitution has been demonstrated to increase the structural stability of sulfur silver germanium ore type sulfides in humid air, which enhancement is attributable to the formation of oxysulfides with high chemical stability, but excessive oxygen substitution would significantly reduce the ionic conductivity. In addition, according to the theory of soft and hard acid base, soft acids tend to react with soft bases and hard acids tend to react with hard bases, thereby forming stable compounds. The phosphorus in the sulfide belongs to hard acid, and can not stably coexist with the sulfur belonging to soft alkali in the sulfide, and the water stability can be effectively improved by replacing the phosphorus with a soft acid element; in addition, the soft acid element with the ionic radius larger than that of the phosphorus ion is selected, so that a lithium ion transmission channel can be enlarged, and the lithium ion conductivity of the solid electrolyte is improved. Notably, oxygen element or soft acid substitution aimed at improving water stability can also improve the compatibility of the sulfur silver germanium ore-type sulfide with metallic lithium.
Patent ZL201810047984.7 discloses a sulfide solid electrolyte, a method for preparing the same and an all-solid-state lithium secondary battery by mixing a certain amount of ZnO or Sb 2 O 5 Double doping modification is carried out on the sulfide solid electrolyte material, so that the air stability and the lithium ion conductivity are improved. However, the dopant used in the binary doping method is a compound containing two doping elements, which is unfavorable for forming uniform components and crystal structures in the mixing and sintering processes, and particularly, under the condition of high doping content or substitution amount, a large amount of impurities are easily generated in the sulfide solid electrolyte, so that the conductivity of the sulfide solid electrolyte is reduced.
Patent ZL201910358953.8 discloses a high air stability inorganic sulfide solid electrolyte, a preparation method and application thereof, and Sb element is adopted to replace part or all of P element in the sulfide electrolyte, so that the solid electrolyte with higher air stability and higher lithium ion conductivity is obtained. However, the method cannot realize comprehensive improvement of the performance of the solid electrolyte on the premise of substituting the single element, and particularly has stability to metallic lithium and compatibility to high-voltage positive electrode materials.
Disclosure of Invention
The invention aims to provide a binary co-doped sulfur silver germanium ore type solid electrolyte and preparation and application thereof, so as to solve the problems of poor air stability and poor stability to metallic lithium of the existing sulfur silver germanium ore type solid electrolyte.
The aim of the invention can be achieved by the following technical scheme: a process for preparing binary Co-doped S-Ag-Ge ore type solid electrolyte includes such steps as preparing lithium sulfide (Li 2 S), phosphorus pentasulfide (P) 2 S 5 ) Mixing with lithium halide (LiX) and grinding uniformly to obtain a stoichiometric ratio of Li 6-x PS 5-x X 1+x Adding the mixed material with x being more than or equal to 0 and less than or equal to 1, and then adding the doping raw material and grinding uniformly to obtain mixed powder; and then the mixed powder is sintered, kept warm for a period of time, cooled to room temperature and ground again to obtain the binary co-doped sulfur silver germanium ore type solid electrolyte powder.
Further, in the mixed powder, the mass percentage of lithium sulfide is 25-45%, the mass percentage of phosphorus pentasulfide is 20-40%, the mass percentage of lithium halide is 15-30%, and the mass percentage of doping raw materials is 5-25%.
Further, the lithium halide comprises lithium chloride, lithium bromide or lithium iodide; the halogen in the lithium halide comprises chlorine, bromine or iodine.
Further, the doping raw material comprises a doping material used for forming a P layer 5+ Site-doping of cations M n+ Compound 1 of (2) and for use in S 2- Site-doping anions Y z- Compound 2 of (a); the two elements of the binary co-doping come from different compounds 1 and 2 respectively, and no elements except lithium, phosphorus and sulfur are introduced, wherein, at P 5+ Site-doped cation M n+ Is greater than the ionic radius of phosphorus, compound 1 comprises M 2 S n Or MS (MS) n/2 Compound 2 comprises Li z Y or P z Y 5 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the compound 1 to the compound 2 is 0.5-5: 1.
further, the doping cation M n+ Comprises Sn 4+ 、As 3+ 、Sb 5+ 、Cu 2+ 、Ce 3+ Or In 3+ The method comprises the steps of carrying out a first treatment on the surface of the Doping anions Y z- Includes F - 、Cl - 、Br - 、I - 、O 2- 、Se 2- Or N 3- 。
Further, the compound 1 comprises SnS 2 、As 2 S 3 、Sb 2 S 5 、CuS、Ce 2 S 3 Or In 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the Compound 2 includes LiF, liCl, liBr, liI, li 2 O、P 2 O 5 、Li 2 Se、P 2 Se 5 Or Li (lithium) 3 N。
Further, the grinding is carried out in a ball milling tank provided with grinding balls; the ball milling tank is made of stainless steel, polytetrafluoroethylene, corundum, polypropylene, nylon, polyurethane or zirconia, and the grinding balls comprise zirconia balls, agate balls, corundum balls or tungsten carbide balls.
Further, the mass ratio of the grinding balls to the balls of lithium sulfide, phosphorus pentasulfide and lithium halide is 1-20: 1, the ball milling rotating speed is 100-500 r min -1 The ball milling time is 0.5-6 h.
Further, the temperature rising rate of the mixed powder sintering is 1-10 ℃ for min -1 The sintering temperature is 300-550 ℃, and the heat preservation time is 3-24 hours.
Further, the mixed powder is sintered in an alumina crucible, a magnesia crucible or a platinum crucible which are nested in a quartz crucible or directly sealed in a quartz tube.
The second object of the present invention is to provide a binary co-doped sulfur silver germanium ore type solid electrolyte prepared by the method, wherein the binary co-doped sulfur silver germanium ore type solid electrolyte is a cubic phase, and the lithium ion conductivity of cold compression tablets is greater than 1mS cm -1 。
The invention further provides application of the binary co-doped sulfur silver germanium ore type solid electrolyte, which is applied to all-solid-state batteries, including metal lithium symmetrical batteries and Liin-NCM811 batteries.
Compared with the prior art, the invention has the following advantages:
1. the two doping elements in the binary co-doped sulfur silver germanium ore type solid electrolyte prepared by the invention come from different compounds, and the mixed powder is obtained by firstly mixing lithium sulfide, phosphorus pentasulfide and lithium halide (LiX) and then grinding uniformly, and then adding doping raw materials and grinding uniformly; then the mixed powder is sintered and kept warm for a period of time and then cooled to room temperature, and the binary co-doped sulfur silver germanium ore type solid electrolyte powder obtained after secondary grinding is a standard cubic phase, and has the advantages of high lithium ion conductivity, easiness in cold press molding and the like;
2. in the preparation process of the binary co-doped sulfur silver germanium ore type solid electrolyte, soft acid element ions with the ionic radius larger than that of phosphorus ions are used for replacing P by adopting a binary co-doping or substitution mode 5+ Sites and anionic substitutions S 2- Sites, soft acid element ions with large ionic radius can widen a lithium ion transmission channel and improve lithium ion conductivity; according to the soft and hard acid-base theory, the soft acid element can effectively improve the air stability of sulfide. While suitable anionic substitution can produce interlayer compositions that are stable to metallic lithium interfaces, resulting in more uniform lithium ion deposition and exfoliation. The anion-cation double substitution plays a role in synergism, and simultaneously enhances the air stability and the stability to metallic lithium of the sulfide silver germanium ore type sulfide solid electrolyte;
3. the two elements of the binary dopant in the binary co-doped sulfur silver germanium ore type solid electrolyte prepared by the method come from different compounds, and elements except lithium, phosphorus and sulfur are not introduced any more, compared with the compound directly using the two doping elements, the method can promote the solid electrolyte to form uniform components and crystal structures in the mixing and sintering processes, and particularly can avoid the problems of conductivity and other electrochemical performance reduction caused by the occurrence of a large amount of impurities in the sulfide solid electrolyte under the condition of high doping content or substitution amount;
4. under the condition of higher content binary co-doping or co-substitution, the binary co-doped sulfur silver germanium ore type solid electrolyte prepared by the method has uniform components and structure, the preparation method is simple and efficient, the solid electrolyte prepared by the method has high lithium ion conductivity and enhanced air stability, the cycle performance of the metal lithium is obviously improved, and the ternary nickel-rich anode material can be matched to form an all-solid-state battery.
Drawings
FIG. 1 is an electron microscope and an element energy spectrum of a tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) prepared in example 1;
FIG. 2 is an electrochemical AC impedance spectrum of the solid electrolyte (SnO-LPSC) prepared in example 2 and doped with lithium phosphorus sulfur chloride;
FIG. 3 is a graph showing the change of lithium ion conductivity with temperature of the solid electrolyte (SnO-LPSC) prepared in example 2 and doped with lithium phosphorus sulfur chloride;
FIG. 4 is a diagram showing the Rietvled fine powder diffraction pattern of the solid electrolyte (SnO-LPSC) of Co-doped lithium phosphorus sulfur chloride with tin oxide prepared in example 3;
FIG. 5 is a Raman spectrum of the solid electrolyte (SnO-LPSC) prepared in example 3 and doped with lithium phosphorus sulfur chloride;
FIG. 6 is a graph showing the long cycle voltage of a metal lithium symmetric battery with a tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) prepared in example 4;
FIG. 7 is a graph showing the cumulative concentration of hydrogen sulfide generated by exposing a solid electrolyte of tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC) prepared in example 5 to humid air;
FIG. 8 is a graph showing the long-cycle discharge capacity and coulombic efficiency of Liin-NCM811 cells of the tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) prepared in example 6;
fig. 9 is a charge-discharge curve of the tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) LiIn-NCM811 cell of the 1 st turn and the 100 th turn prepared in example 6;
fig. 10 is a powder diffraction pattern of a tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) prepared according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the invention. These are all within the scope of the present invention.
The reagents used in the following examples were all commercially available, with lithium sulfide (99.9% purity) available from Ganfeng lithium company; phosphorus pentasulfide (99% purity) was purchased from michelter chemical company; lithium carbonate, lithium chloride, lithium bromide, and lithium iodide (purity 99%, anhydrous grade) were purchased from Shanghai Ala Biochemical technologies Co., ltd; the doping materials include tin disulfide, phosphorus pentoxide, lithium oxide, etc. (purity 99.99%) purchased from Shanghai Ala Biochemical technologies Co., ltd. The various devices used in the examples below are all commercially available devices.
Example 1
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 35%, 30% and 30%, respectively, using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 3, and the mixing speed is 100r min -1 Ball milling for 6 hours at the rotating speed, then adding 5 percent of doping raw materials including tin disulfide and phosphorus pentoxide with the mol ratio of 2.5 into the mixture for 100r min -1 Ball milling was carried out at a rotational speed of (3) hours, followed by separating zirconia balls from the mixed powder using a stainless steel screen. Sealing the mixed powder in quartz tube for sintering at 1deg.C for min -1 Is heated to 500 ℃ and is cooled to room temperature along with a muffle furnace after being kept for 16 hours. Stainless steel ball milling pot using zirconia balls and zirconia substrate, re-milling the sintered powder at 200r min -1 Ball milling for 2 hours at the rotating speed to obtain the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC) solid electrolyte.
The electron micrograph and the element energy spectrum of the SnO-LPSC solid electrolyte powder prepared in this example are shown in fig. 1, the particle size of the solid electrolyte is 5-10 μm, and the distribution of various elements including doping elements is very uniform by using two independent dopants as a binary co-doping raw material.
Example 2
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 30%, 30% and 30%, respectively, using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 2, and the ball-to-material ratio is 300r min -1 Ball milling for 1 hour at a rotating speed of (2) and then adding 10% by mass of doping raw materials including tin disulfide and lithium oxide with a molar ratio of 0.5 at 300r min -1 Ball milling was performed for 0.5 hours at a rotational speed, followed by separating zirconia balls and the mixed powder using a stainless steel screen. Placing the mixed powder into an alumina crucible nested in a quartz crucible for sintering, wherein the sintering procedure is that the temperature is 10 ℃ for min -1 Is heated to 450 ℃ and is cooled to room temperature along with the furnace after being kept for 10 hours. Stainless steel ball milling pot using zirconia balls and zirconia substrate, re-milling the sintered powder at 300r min -1 Ball milling is carried out for 0.5 hour at the rotating speed to obtain the solid electrolyte of the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC).
The electrochemical AC impedance spectrum of the SnO-LPSC solid electrolyte powder prepared in this example is shown in FIG. 2, the lithium ion conductivity test condition of the solid electrolyte cold-pressed sheet body is an external load pressure of 250MPa, the impedance spectrum exhibits a linear tailing by using a carbon-coated aluminum foil as a symmetric ion blocking electrode, since the bulk and grain boundary resistances of a sulfide solid electrolyte having high ion conductivity are limited to the maximum frequency (13 MHz) of the test instrument and the conductivity of the solid electrolyte is 8.7mS cm, which can be measured from the intersection point of the impedance spectrum curve and the real axis -1 . The curve of the lithium ion conductivity of the SnO-LPSC solid electrolyte powder prepared in this example with temperature change is shown in fig. 3, the logarithm of the lithium ion conductivity and the reciprocal of the temperature have a good linear relationship, conform to the arrhenius relationship, and the calculated activation energy is 0.18eV.
Example 3
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to the mass fractions of 40%, 30% and 20%, and using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 3, and the speed is 100r min -1 Ball milling for 6 hours at the rotating speed of (2)Then adding 10% of doping raw materials including tin disulfide and phosphorus pentoxide with a molar ratio of 2, and adding the mixture into the mixture for 100r min -1 Ball milling was carried out at a rotational speed of (3) hours, followed by separating zirconia balls from the mixed powder using a stainless steel screen. Placing the mixed powder into an alumina crucible nested in a quartz crucible for sintering, wherein the sintering procedure is that the temperature is 5 ℃ for min -1 Is heated to 470 ℃ and is cooled to room temperature along with the furnace after being kept for 20 hours. Stainless steel ball milling pot using zirconia balls and zirconia substrate, re-milling the sintered powder at 500r min -1 Ball milling is carried out for 0.5 hour at the rotating speed to obtain the solid electrolyte of the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC).
The powder diffraction pattern of the SnO-LPSC solid electrolyte prepared in this example is shown in fig. 4, and a cubic phase of sulfur silver germanium ore type, whose unit cell parameter is a=b=c= 0.9801nm, was obtained by refining using Rietveld, and whose phase is standard, was free from occurrence of a second phase or other impurities by using two independent dopants as a binary co-doped raw material. The Raman spectrum of the SnO-LPSC solid electrolyte prepared in this example is shown in FIG. 5, the main peak is located at 429cm -1 PS of (c) 4 3- Symmetrical stretching vibration peak due to Sn 4+ P pair P 5+ Is positioned at 346cm -1 SnS of (2) 4 4- Is a stretching vibration peak of (2).
Example 4
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 35%, 30% and 20%, and using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 2, and the ball-to-material ratio is 300r min -1 Ball milling for 1 hour at a rotating speed, then adding 15% of doping raw materials including tin disulfide and lithium oxide in a molar ratio of 1, and performing ball milling for 300r min -1 Ball milling was performed for 0.5 hours at a rotational speed, followed by separating zirconia balls and the mixed powder using a stainless steel screen. Placing the mixed powder into an alumina crucible nested in a quartz crucible for sintering, wherein the sintering procedure is that the temperature is 5 ℃ for min -1 Is heated to 470 ℃ and is cooled to room temperature along with the furnace after being kept for 20 hours. Using oxidationStainless steel ball milling pot for zirconium balls and zirconium oxide substrate, re-milling sintered powder, and grinding for 500r min -1 Ball milling is carried out for 0.5 hour at the rotating speed to obtain the solid electrolyte of the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC).
The step of assembling the tin-oxygen co-doped lithium phosphorus sulfur chloride (SnO-LPSC) solid electrolyte prepared in the embodiment into a metal lithium symmetrical battery comprises the steps of firstly cold pressing solid electrolyte powder into a sheet with the diameter of 12mm and the thickness of 1mm under the uniaxial pressure of 250MPa, attaching metal lithium sheets on two sides of the cold pressed sheet, and obtaining a compact interface under the uniaxial pressure of 50MPa to obtain the Li/SnO-LPSC/Li button battery. The long cycle voltage curve of the metal lithium symmetric cell of the SnO-LPSC solid electrolyte prepared in this example is shown in FIG. 6, and the electrochemical stability of the solid electrolyte to metal lithium is enhanced by using two independent dopants as the raw materials for binary co-doping, which can be respectively 0.25 and 0.5mA cm -2 Is cycled for 200 hours at a current density of 8mV (32 Ω cm) -2 ) The voltage plateau after 200 hours of lithium deposition stripping was 10mV (40. OMEGA cm -2 ) Has excellent interfacial compatibility.
Example 5
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 35%, 25% and 25%, respectively, using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 3, and the speed is 100r min -1 Ball milling for 6 hours at the rotating speed, then adding 15 percent of doping raw materials including tin disulfide and phosphorus pentoxide with the mol ratio of 1.5 into the mixture for 100r min -1 Ball milling was carried out at a rotational speed of (3) hours, followed by separating zirconia balls from the mixed powder using a stainless steel screen. Placing the mixed powder into an alumina crucible nested in a quartz crucible for sintering, wherein the sintering procedure is that the temperature is 10 ℃ for min -1 Is heated to 450 ℃ and is cooled to room temperature along with the furnace after being kept for 10 hours. Stainless steel ball milling pot using zirconia balls and zirconia substrate, re-milling the sintered powder at 300r min -1 Ball milling for 0.5 hour at the rotating speed to obtain the solid electricity of the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC)And (5) a electrolyte.
The cumulative concentration curve of hydrogen sulfide produced by exposing the SnO-LPSC solid electrolyte prepared in this example to humid air is shown in fig. 7, and the sulfide solid electrolyte reacts with water to produce harmful hydrogen sulfide gas, and simultaneously, the electrolyte composition and structure are degraded, so that the air stability of the sulfide solid electrolyte can be compared by the cumulative concentration of hydrogen sulfide. By using two independent dopants as the binary co-doped raw materials, the air stability of the solid electrolyte is enhanced, and the cumulative concentration of hydrogen sulfide is significantly reduced compared with the undoped sample.
Example 6
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 30%, 25% and 25%, respectively, using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 2, and the ball-to-material ratio is 300r min -1 Ball milling for 1 hour at a rotating speed of 20% by mass of doping raw materials including tin disulfide and lithium oxide with a molar ratio of 0.5 at 300r min -1 Ball milling was performed for 0.5 hours at a rotational speed, followed by separating zirconia balls and the mixed powder using a stainless steel screen. Sintering the powder in an alumina crucible nested in a quartz crucible at 5 ℃ for a period of min -1 Is heated to 500 ℃ at a temperature rising rate, is kept for 16 hours, and is cooled to room temperature along with the furnace. Stainless steel ball milling pot using zirconia balls and zirconia substrate, re-milling the sintered powder at 500r min -1 Ball milling is carried out for 0.5 hour at the rotating speed to obtain the solid electrolyte of the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC).
The procedure of assembling the tin-oxygen co-doped lithium phosphorus sulfur chloride (SnO-LPSC) solid electrolyte prepared in the above example into a LiIn-NCM811 battery comprises cold pressing solid electrolyte powder into a sheet with a diameter of 12mm and a thickness of 1mm under a uniaxial pressure of 250MPa, uniformly distributing 11mg of composite positive electrode powder (containing 70% NCM811 and 30% SnO-LPSC by mass fraction) on one side of the cold pressed sheet, and an active material loading of 5mg cm -2 Obtaining a tight interface at a uniaxial pressure of 250 MPa; sequentially attaching gold on the other side of the cold-pressed sheetBelongs to an indium sheet and a lithium sheet, and obtains a compact interface under the uniaxial pressure of 50MPa, thus obtaining the LiIn/SnO-LPSC/NCM811 die type (Swagelok) battery. The long-cycle discharge capacity and coulombic efficiency of the SnO-LPSC solid electrolyte Liin-NCM811 battery prepared in this example are shown in FIG. 8, and charge and discharge are performed at a rate of 0.5C, with a cut-off voltage range of 2.2-3.7V vs Liin, corresponding to 2.8-4.3V vs Li/Li + The initial discharge capacity of the battery was 103.6mAh g -1 At turn 100, 101.4mAh g remained -1 The discharge capacity of the product is as high as 97.9%. The charge and discharge curves of the 1 st turn and the 100 th turn of the SnO-LPSC solid electrolyte Liin-NCM811 battery prepared in this example are shown in FIG. 9, and the polarization of the battery is increased, but the capacity of the battery has a higher retention rate.
The powder diffraction pattern of the tin-oxygen co-doped lithium phosphorus sulfur chlorine solid electrolyte (SnO-LPSC) prepared by the invention is shown in figure 10, wherein the diffraction peak of the solid electrolyte shows that the solid electrolyte belongs to sulfur silver germanium ore type family compounds (representative compounds are Li) 7 PS 6 Or Li (lithium) 6 PS 5 Cl), no impurity peak, shows that the binary doping mode adopted by the invention can effectively drive the doping elements to be uniformly mixed and doped into the lattice. The low angle swell peaks are from Kapton films, which are used to protect the diffraction tested sulfide powders from exposure to air atmosphere.
Example 7
In an argon environment, sequentially weighing lithium sulfide, phosphorus pentasulfide and lithium chloride according to mass fractions of 25%, 20% and 30%, and using a stainless steel ball grinding tank with zirconia balls and a zirconia substrate, wherein the ball-to-material ratio is 20, and the ball-to-material ratio is 100r min -1 Ball milling for 6 hours at the rotating speed, then adding 25 percent of doping raw materials including tin disulfide and phosphorus pentoxide with the mol ratio of 5 into the mixture for 100r min -1 Ball milling was carried out at a rotational speed of (3) hours, followed by separating zirconia balls from the mixed powder using a stainless steel screen. Sealing the mixed powder in quartz tube for sintering at 10deg.C for min -1 Is heated to 550 ℃, is kept for 3 hours and is cooled to room temperature along with a muffle furnace. Using zirconia balls and oxygenStainless steel ball grinding pot of zirconium oxide substrate, grinding sintered powder again, and grinding for 100r min -1 Ball milling for 2 hours at the rotating speed to obtain the tin-oxygen co-doped lithium phosphorus sulfur chlorine (SnO-LPSC) solid electrolyte.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. A process for preparing binary co-doped sulfur silver germanium ore type solid electrolyte is characterized by mixing lithium sulfide, phosphorus pentasulfide and lithium halide LiX and grinding uniformly to obtain a stoichiometric ratio of Li 6-x PS 5-x X 1+x Adding the mixed material with x being more than or equal to 0 and less than or equal to 1, and then adding the doping raw material and grinding uniformly to obtain mixed powder; and then the mixed powder is sintered, kept warm, cooled to room temperature and ground again to obtain the binary co-doped sulfur silver germanium ore type solid electrolyte powder.
2. The preparation method of the binary co-doped sulfur silver germanium ore type solid electrolyte according to claim 1, wherein in the mixed powder, the mass percentage of lithium sulfide is 25-45%, the mass percentage of phosphorus pentasulfide is 20-40%, the mass percentage of lithium halide is 15-30%, and the mass percentage of doping raw materials is 5-25%.
3. The method for preparing the binary co-doped sulfur silver germanium ore type solid electrolyte according to claim 1, wherein the lithium halide comprises lithium chloride, lithium bromide or lithium iodide.
4. A binary co-doped silver sulfide according to claim 1The preparation method of the germanium ore type solid electrolyte is characterized in that the doping raw material comprises the following steps of 5+ Site-doping of cations M n+ Compound 1 of (2) and for use in S 2- Site-doping anions Y z- Compound 2 of (a).
5. The method for preparing a binary co-doped sulfur, silver and germanium ore type solid electrolyte according to claim 4, wherein the compound 1 comprises SnS 2 、As 2 S 3 、Sb 2 S 5 、CuS、Ce 2 S 3 Or In 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the Compound 2 includes LiF, liCl, liBr, liI, li 2 O、P 2 O 5 、Li 2 Se、P 2 Se 5 Or Li (lithium) 3 N; the molar ratio of the compound 1 to the compound 2 is 0.5-5: 1.
6. the method for preparing the binary co-doped sulfur silver germanium ore type solid electrolyte according to claim 1, wherein the grinding is performed in a ball milling tank provided with grinding balls; the ball milling tank is made of stainless steel, polytetrafluoroethylene, corundum, polypropylene, nylon, polyurethane or zirconia, and the grinding balls comprise zirconia balls, agate balls, corundum balls or tungsten carbide balls.
7. The preparation method of the binary co-doped sulfur silver germanium ore type solid electrolyte according to claim 6, wherein the mass ratio of the grinding balls to the balls of lithium sulfide, phosphorus pentasulfide and lithium halide is 1-20: 1, the ball milling rotating speed is 100-500 r min -1 The ball milling time is 0.5-6 h.
8. The method for preparing the binary co-doped sulfur silver germanium ore type solid electrolyte according to claim 1, wherein the temperature rising rate of the mixed powder sintering is 1-10 ℃ for min -1 Sintering temperature is 300-550 ℃, and heat preservation time is 3-24 h; the mixed powder is sintered in an alumina crucible nested in a quartz crucibleIn a magnesia crucible or a platinum crucible or directly sealing the mixed powder in a quartz tube.
9. The binary co-doped sulfur silver germanium ore type solid electrolyte prepared by the method of claim 1, which is characterized in that the binary co-doped sulfur silver germanium ore type solid electrolyte is in a cubic phase.
10. The use of a binary co-doped sulfur, silver, germanium ore-type solid electrolyte according to claim 9, wherein the binary co-doped sulfur, silver, germanium ore-type solid electrolyte is used in an all-solid-state battery.
CN202211543685.5A 2022-11-30 2022-11-30 Binary co-doped sulfur silver germanium ore type solid electrolyte and preparation and application thereof Pending CN116154273A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117594866A (en) * 2023-10-25 2024-02-23 浙江大学 Sulfur nitride solid electrolyte and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117594866A (en) * 2023-10-25 2024-02-23 浙江大学 Sulfur nitride solid electrolyte and preparation method and application thereof
CN117594866B (en) * 2023-10-25 2024-06-04 浙江大学 Sulfur nitride solid electrolyte and preparation method and application thereof

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